US3290276A - Oil-soluble phospho-halo-containing ethylene/propylene copolymers - Google Patents

Description

3,290,276 OIL-SOLUBLE PHGSIHG-HALQ-CONTAINING ETHYLENE/PRGPYLENE COPOLYMERS William S. Anderson, Oakland, Calif., assignor to Shell Oil Company, a corporation of Delaware No Drawing. Original application Dec. 21, 1959, Ser. No. 860,716, new PatentNo. 3,105,819. Divided and this application May 3, 1963, Ser. No. 277,705

3 Claims. (Cl. 260--88.2)

This patent application is a division of c-opending case, Serial No. 860,716, filed December 21, 1959, and is now U.S. Patent 3,105,819.

This invention relates to a new and novel class of polymers. More particularly the invention is directed to multifunctional polymers containing a plurality of phosphor-us units attached to a long hydrocarbon back bone chain.

In the field of lubrication non-ash forming polymeric detergent extreme pressure additives are particularly desirable although copolymers of this invention have many other applications as will be shown hereinbelow.

It has been discovered that polymers which meet this requirement are oil-soluble copolymers of the present invention which are polyphosphonated copolymers of ethylone and a lower monoalkyl ethylene such as copolymers of ethylene and propylene or ethylene and bute-n-e-l or mixtures thereof. In copolymers of this invention the ethylene precurser comprises at least 20% of the total mixture at least 10% and preferably 15-40% of the phosphonated copolymer product. The phosphonated copolymer has a plurality of units represented by:

units, normally if present vary from about 2% to about 15% of units (1). Copolymers of this invention range in molecular weight from about 5,000 to about 1,000,000, preferably between about 100,000 and about 500,000. The symbols in the above formulas are: R is a C alkyl radical, preferably a CH radical, the Xs can be --YR' and where Y is oxygen or sulfur and R is -a hydrocarbyl radical, such as C prefer-ably C alkyl, cycloalkyl, aralkyl radical or a cation such as amine, e.g. C alkyl amine, polyamine, e.g. an alkylene diamine, a heterocyclic amine, e.g. alkyl substituted pyridine, etc.

The phosphonated copolymers of the present invention are prepared by reacting ethylene and a lower monoalkyl ethylene such as propylene, butene-l and the like to form copolymers such as ethylene/propylene copolymer made by the procedures and techniques described in Irish patent application 695/56 and treating said copolymer with phosphorus chloride under oxidizing conditions, such as by blowing air or oxygen through the reaction mixture under controlled temperature conditions. In essence the intermediate product, that is the elastomeric copolymer, is produced by polymerizing a mixture of ethylene and propylene in the presence of an inert hydrocarbon solvent with a catalyst of the Ziegler type which essentially is a reaction product of a metallo-alkyl compound of Groups I, II or III and a metal halide such as vanadium chloride or vanadium oxychloride. The ratio of ethylene and propylene monomers that is maintained during the polymerization will vary depending on the proportion of the United States Patent 0 elastomer.

Patented Dec. 6, 1966 respective monomers desired in the final elastomer. In the preferred embodiments the elastomer may contain from about 20 mole percent of about mole percent, preferably 30-80 mole percent of ethylene units in the copolymer and still be useful in the formation of the Because the monomers do not polymerize at the same rate, i.e. ethylene polymerizes faster than propylene, the ratio of the starting mixture of monomer is not the same as that desired in the final product and this is one of the major considerations in selecting the starting monomer ratios to give a particular final product. Other considerations are the choice of catalyst components and their respective proportions and the polymerization conditions. By way of illustration, Table I indicates variations of ethylene units in the final elastomer as the ratio of ethylene to propylene in the starting monomer mixture is varied. For this table, polymerizations were conducted at 45-65 C. in n-heptane solvent and the catalyst was the reaction product of-trihexyl-aluminum and vandium oxychloride in a mole ratio of 3.011.

Table I Mole percent Ethylene in Feed Gases Other suitable alkyl aluminum compounds as the catalyst component include trioctyl aluminum, trinonyl aluminum, tridecyl aluminum, triiso-butyl aluminum, and others. Preferably the alkyl radicals of the trialkyl aluminum have more than 4 carbon atoms but not more than 16 carbon atoms. For economic reasons, the number of carbon atoms in the alkyl radicals preferably range from 4 to 10. The ratio of the aluminum compounds to the vanadium oxychloride or vanadium tetrachloride may vary widely but preferably the aluminum to vanadium mole ratio is greater than 2. The catalyst is simply prepared by mixing and reacting the catalyst components in a hydrocarbon solvent whereupon there is formed a reaction product which is the catalyst.

The final phosphorus-containing polymeric product of this invention is obtained by reacting an elastomeric ethylene-propylene copolymer of the type described above with phosphorus trichloride, phosphorus oxychloride, phosphor-us tribromide, etc. in an inert solvent under oxidizing conditions, such as by blowing air or oxygen through the mixture at controlled temperatures of from about 0 to 60 C., preferably at 1035 C. The resulting polyph-osphonyl halide-containing copolymer can be hydro lyzed to form the polyphosphonic acid and the acid esterified or converted into salts by suitable means. The time required for completing the reaction depends upon the number of units (1) which are desired to be provided in the copolymer as well as the ratio of the reactants and the reaction temperature. In general, the time required to complete the reaction may vary from 2 to 48 hours or more.

The following examples are given as illustrative of the present invention.

EXAMPLE I To a mixture of 222 grams of Ziegler type copolymer of 50% ethylene and 50% propylene having an intrinsic viscosity of 5.5 dl./ g. in 2.8 liters of benzene was added dropwise 365 grams of PCI, over a period of 3 hours while simultaneously bubbling oxygen through the mixture and controlling the temperature of the reaction at 1234 C. by ice cooling the reaction vessel. About 550 ml. of methanol was then slowly added, and the resulting HCI swept out with nitrogen. To the product about 1 gram of a phenolic anti-oxidant [2,2-methylene bis(4-methyl- 6-tert.butylphenol)] was added as well as 625 ml. of pyridine and the entire mixture was cooled and allowed to stand for 48 hours. The pyridine salts were filtered off and the polymer precipitated by adding methanol and then reprecipitated three times from benzene into methanol. On analysis the resulting mixed methyl phosphonatephosphonyl chloride containing ethylene/propylene copolymer contained 2.41% phosphorus and 0.983% chloride corresponding to 14% of the ethylene/propylene copolymer units containing the phosphono group.

Following the above procedure, the following phosphono-modified elastomeric copolymers oat ethylene/propylene having an intrinsic viscosity in the range of l to 10 dl./ g. were prepared:

II. Poly(dibutylphosphonate) of ethylene/propylene copolymer having intrinsic viscosity of 2 d1./ g.

III. Poly(dihexylphosphonate) of ethylene/propylene cpolymer having intrinsic viscosity of 34 dl./ g.

IV. Poly(dilaurylphosphonate) of ethylene/ propylene copolymer having intrinsic viscosity of dl./ g.

V. P0ly(stearyl acid phosphonate) of ethylene/ propylene copolymer having intrinsic viscosity of 2 dl./ g.

VI. Poly(dicyclohexyl phosphonate-phosphonylchloride) ethylene/butene-l copolymer having an intrinsic viscosity of 4-6 dl./ g.

The polymeric compounds of this invention are eifective oil additives imparting to lubricants detergency and wear inhibiting properties. Also, they may be used as ion exchange resins, fire-resistent materials, adhesives, coatings, as insecticidal materials, alone or in conjunction with other well known insecticidal agents such as DDT, DDD, aldrin, parathion, Chlorothion and the like. However, polymers of the present invention are outstanding for their ability to impart to mineral oil (1) detergency as determined by the Carbon Black Dispersency Test described in the Journal of Colloid Science, vol. 12, October 1957, No. 5, pages 500522; at 100 C. and 5 r.p.m. and (2) anti-wear properties using Oldsmobile Tappet Wear Test Ring under GMMS Test conditions (2500 r.p.m., 300 number valve open spring load described in the AMA proposed specification for evaluation of oils for API Service classification MS presented at SAE meeting, Atlantic City, New Jersey, June 1958). The results are shown in Table II and the compositions tested were as follows:

Percent Composition A:

Example I additive 2. 1010 neutral mineral oil Essentially balance. Composition B:

Example 11 additive 2.

1010 neutral mineral oil Essentially balance. Composition C:

Example III additive 2 1010 mineral oil a Essentially balance.

Composition D:

Di-2-ethyl hexyl sebacate Essentially balance.

Composition H:

Example I additive 5.. Ucon 50HB660 (polyethylenepropylene glycol having a SUS viscosity at F. of 660) Essentially balance. Composition 1:

Example I additive 5. Di-2-ethylhexyl sebacate Essentially balance.

Table II GM-MS Test Detergency Composition (deflocculating Av. Av. Cam

ability) lifter B wear,

visual thourating sands of inch (1) 100 Neutral mineral oil 3 X 10 ohms. 5 44 (2) (1) 2% Ca petroleum 3.3 X 10 ohms 5 44 sulfonate. ans alkyl 3 X 10 ohms 5 44 methacrylate copolymer. (4) Compositions A-I (present 12 X 10 ohms 9 0 invention).

10=perfect.

From the test results the superiority of compositions of the present invention to oils containing convention detergents (2) or polymers (3) with respect to detergency, cleanliness and wear inhibition is clearly evidenced. Thus, representative compositions of the present invention (4) is about 4 times as effective as a detergent as are compositions (2) and (3) or a neat oil (1), twice as effective in preventing sludge and many more times effective as a wear inhibitor than that of compositions (1), (2) or (3).

The polymers of this invention are useful also for providing superior load-carrying properties in lubricating oils which contain minor amounts of other agents which are non-reactive with the polymer, such as silicone anti-foaming agents, alkylphenol anti-oxidants, polyacrylate ester viscosity-index improvers, and the like.

I claim as my invention:

1. An oil-soluble polyphosphonate of ethylene/propylene copolymer, the phosphonate units in the copolymer being represented by RO/ \OR where R is an alkyl selected from the group consisting of lauryl and stearyl radicals and the number of such units comprise from 10% to 40% of the ethylene/propylene copolymer, said copolymer having a molecular weight of from 5000 to 1,000,000.

2. The copolymer of claim 1 wherein R is lauryl and the mole percent of ethylene is 30-80 mole percent and the balance is propylene.

3. The copolymer of claim 1 wherein R is stearyl and the mole percent of ethylene is 30-80 mole percent and the balance is propylene.

References Cited by the Examiner UNITED STATES PATENTS 3,008,939 11/1961 Schroeder et al. 260-94.9 3,023,180 2/1962 Canterino et al. 260-949 JOSEPH L. SCHOFER, Primary Examiner. L. E. DELMAN, Assistant Examiner.

Claims (1)

1. AN OIL-SOLUBLE POLYPHOSPHONATE OF ETHYLENE/PROPYLENE COPOLYMER, THE PHOSPHONATE UNITS IN THE COPOLYMER BEING REPRESENTED BY